WO2018149844A1

WO2018149844A1 - Polyoxazolidones and production thereof

Info

Publication number: WO2018149844A1
Application number: PCT/EP2018/053612
Authority: WO
Inventors: Hans-Josef Thomas; Markus Schuette; Berend Eling; Patrick Matt
Original assignee: Basf Se
Priority date: 2017-02-16
Filing date: 2018-02-14
Publication date: 2018-08-23
Also published as: EP3583148A1; JP7317707B2; US11180603B2; ES2874003T3; CN110300772B; KR20190112270A; KR102587180B1; BR112019015243A2; JP2020508359A; US20190359757A1; RU2019128899A; RU2019128899A3; EP3583148B1; CN110300772A

Abstract

The invention relates to a thermoplastic polymer produced at least from diisocyanate and diepoxide using a catalyst, wherein the catalyst is an ionic liquid. The invention also relates to associated production methods and uses.

Description

Polyoxazolidones and their preparation

DESCRIPTION The present invention relates to a thermoplastic polymer based on diisocyanate and diepoxide, which is also referred to as polyoxazolidone.

The preparation of polyoxazolidones based on diisocyanate and diepoxide is known in principle. The focus is usually directed to networked structures, as they are mentioned for example in DE 10 2014 226 838 A1. In this case, starting from the isocyanate and epoxide, a number of secondary reactions occur, which have an adverse effect on the thermoplastic properties of the polyoxozolidones.

The synthesis of linear polyoxazolidones is described in documents WO 2015/1731 11 A1, WO 2015/173 1 10 A1, US 2014/012 1299, DE 10 2014 226 838 A1 and WO 2014/076024 A1. However, the catalysts described herein do not involve the use of ionic liquids as catalyst.

It was therefore an object of the present invention to provide thermoplastic polyoxazolidones in which the side reactions occur only to a slight extent, so as not to adversely affect the properties, in particular the thermoplastic property of the polyoxazolidone.

Surprisingly, the product properties, in particular the thermoplastic property of polyoxazolidones, could be significantly improved by preparing the polyoxazolidone with a suitable catalyst, which may also be present in the end product.

The present invention thus provides a polymer prepared at least from diisocyanate, diepoxide using a catalyst, wherein the catalyst is an ionic liquid.

Another object of the invention is the preparation of this polymer and its use.

Detailed Description Diepoxide

The diepoxides are epoxides having preferably exactly two epoxide groups per molecule. These epoxides may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic. You can still use such substituents contain, which cause no adverse side reactions under the reaction conditions, for example, alkyl or aryl substituents, ether moieties and the like.

The diepoxides are preferably polyglycidyl ethers based on dihydric alcohols, phenols, hydrogenation products of these phenols and / or novolaks. Novolacs are reaction products of phenols with aldehydes, in particular formaldehyde, in the presence of acidic catalysts, the diglycidyl ethers being particularly preferred. However, diepoxides based on other structures which do not contain any ether groups are also possible.

Other preferred diepoxides are based on diglycidyl ethers of natural raw materials, preferably cardanol. A typical example of such a product is Cardolite NC 514 (Cardolite). The advantage of this epoxide is the longer alkyl chain between the aromatics which leads to a higher flexibility of the polymers produced therefrom. The advantages of aliphatic structural elements in combination with aromatic diglycidyl ethers are particularly pronounced. Therefore, diepoxides based on aliphatic diglycidyl ethers in combination with aromatic diglycidyl ethers are particularly preferred.

The epoxide equivalent weights (EEW) of these epoxy compounds are preferably between 100 and 5000, in particular between 150 and 500. The epoxide equivalent weight of a substance is defined as that amount of substance (in grams) containing 1 mole of oxirane rings. The method of determination is described in the examples.

Suitable polyhydric phenols are preferably the following compounds: resorcinol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), isomer mixtures of dihydroxydiphenylmethane (bisphenol F), tetrabromobisphenol A, 4,4'-dihydroxy -diphenylcyclohexane, 4,4'-dihydroxy-3,3-dimethyldiphenylpropane, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxybenzophenol, bis (4-hydroxyphenyl) -1, 1-ethane, bis- (4-hydroxyphenyl) -1, 1 -isobutane, bis (4-hydroxyphenyl) -methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone and others and the chlorination and bromination products of the aforementioned compounds; Bisphenol A is particularly preferred. Commercially available products for bisphenol A diglycidyl ether include DER 331, DER 330 from DOW U.S.A., or Epilox A18-00 from Leuna Harz, Germany. isocyanates

In the present case, the diisocyanate is understood as meaning both a single substance and a mixture of substances, which is preferably selected from the list below. The diisocyanates are preferably organic isocyanates, further preferred are aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, which are more preferably selected from the group tri, tetra, penta, hexa, hepta and / or Oktamethylendiisocya- nat, 2-methyl-pentamethylene-diisocyanate-1, 5, 2-ethyl-butylene-diisocyanate-1, 4, pentamethylene-diisocyanate-1, 5, butylene-diisocyanate-1, 4, 1-isocyanato-3, 3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis (isocyanatomethyl) cyclohexane (HXDI), 1,4-cyclohexane diisocyanate, 1-methyl -2,4- and / or -2,6-cyclohexane diisocyanate, 4,4'-, 2,4'- and / or 2,2'-dicyclohexylmethane diisocyanate, 2,2'-, 2,4 ' and / or 4,4'-diphenylmethane diisocyanate (MDI), 1, 5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-toluene diisocyanate (TDI), diphenylmethane diisocyanate, 3,3'- Dimethyl-diphenyl-diisocyanate, 1,2-diphenyl-1-diisocyanate, 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate (H12 MDI), 2,4-paraphenylene diisocyanate (PPDI), 2,4-Tetramethylenxylendiisocyant (TMXDI) preferably 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI) and / or 1, 6-hexamethylene diisocyanate (HDI).

Preferred are aromatic diisocyanates selected from the above list. More preferably, the isocyanate is selected from the group toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and 1, 5-naphthylene diisocyanate (NDI). Very particular preference is given to tolylene diisocyanate (TDI) or diphenylmethane diisocyanate (MDI).

catalyst

The catalysts used for the preparation of the thermoplastic polymer are ionic liquids,

Ionic liquids are organic salts whose ions hinder the formation of a stable crystal lattice through charge delocalization and steric effects. Even low thermal energy is therefore sufficient to overcome the lattice energy and break up the solid crystal structure. They are thus salts which are liquid at temperatures below 250 ° C., preferably below 200 ° C. and particularly preferably below 150 ° C., without the salt or the like being dissolved in a solvent such as water or the like. is solved.

Preferably, the cations of the ionic liquid are alkylated, and more preferably selected from the group consisting of imidazolium, pyridinium, pyrrolidinium, guanidinium, uronium, thiouronium, piperidinium, morpholinium, ammonium and phosphonium. The anions in the ionic liquid are preferably halides or complex ions, which are preferably selected from the group: tetrafluoroborate, trifluoroacetate, triflate, hexafluorophosphate, phosphinate and tosylate. In another preferred embodiment, the anions are organic ions, preferably imides or amides.

Ionic liquids in the context of the present invention are preferably salts of the general formula

(A) Salts of the general formula (I)

[A] "[ΥΓ (i),

where n is 1, 2, 3 or 4, [A] ^{+ is} a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation, and [Y] ^{n_ is} a bi-, tri- or tetravalent anion is; or (B) mixed salts of the general formulas (II)

[A] ⁺ [A ² ] ⁺ [Y] ⁿ - (IIa), where n = 2;

[A] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] ⁿ - (IIb), where n = 3; or

[A] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [A] ⁺ [Y] ⁿ - (llc), where n = 4 and

where [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ⁺ independently of one another are those mentioned for [A] ⁺

Groups are selected and [Y] ⁿ - has the meaning mentioned under (A); or

(C) mixed salts of the general formulas (III)

[A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [M ¹ ] ⁺ [Y] ⁿ - la), where n = 4;

[A ¹ ] ⁺ [A ² ] ⁺ [M ¹ ] ⁺ [M ² ] ⁺ [Y] ⁿ - Ib), where n = 4;

[A] ⁺ [M] ⁺ [M ² ] ⁺ [M ³ ] ⁺ [Y] ⁿ - Ic), where n ^■ 4;

[A] ⁺ [A ² ] ⁺ [M] ⁺ [Y] ⁿ - Id), where n = 3;

[A] ⁺ [M] ⁺ [M ² ] ⁺ [Y] ⁿ - le), where n = 3;

[A] ⁺ [M] ⁺ [Y] ⁿ - If), where n is 2;

[A ¹ ] ⁺ [A ² ] ⁺ [M ⁴ ] ²⁺ [Y] ⁿ -Ig), where n = 4;

[A ¹ ] ⁺ [M ¹ ] ⁺ [M ⁴ ] ²⁺ [Y] ⁿ - Ih), where n = 4;

[A ¹ ] ⁺ [M ⁵ ] ³⁺ [Y] ⁿ - Ii), where n ^: 4; or

[A ¹ ] ⁺ [M ⁴ ] ²⁺ [Y] ⁿ - IIj), where n = 3 and

where [A ¹ ] ⁺ , [A ² ] ⁺ and [A ³ ] ^{+ are selected} independently of one another from the groups mentioned for [A] ⁺ , [Y] ⁿ - has the meaning mentioned under (A) and [M ¹ ] ⁺ , [M ² ] ⁺ , [M ³ ] ⁺ monovalent metal cations, [M ⁴ ] ²⁺ divalent metal cations and [M ⁵ ] ³⁺ trivalent metal cations.

Compounds suitable for forming the cation [A] ⁺ of ionic liquids are e.g. B. from DE 102 02 838 A1. Thus, such compounds may contain oxygen, phosphorus, sulfur or in particular nitrogen atoms, for example at least one nitrogen atom, preferably 1-10 nitrogen atoms, particularly preferably 1-5, very particularly preferably 1-3 and in particular 1-2 nitrogen atoms. Optionally, other heteroatoms such as oxygen, sulfur or phosphorus atoms may be included. The nitrogen atom is a suitable carrier of the positive charge in the cation of the ionic liquid, from which, in equilibrium, a proton or an alkyl radical can then be transferred to the anion in order to produce an electrically neutral molecule.

In the event that the nitrogen atom is the carrier of the positive charge in the cation of the ionic liquid, in the synthesis of the ionic liquids, a cation can first be generated by quaternization on the nitrogen atom of, for example, an amine or nitrogen heterocycle. The quaternization can be carried out by alkylation of the nitrogen atom. Depending on the alkylating reagent used, salts with different anions are obtained. In cases where it is not possible to form the desired anion already during the quaternization, this can be done in a further synthesis step. Starting, for example, from an ammonium halide, the halide can be reacted with a Lewis acid, wherein Halide and Lewis acid is a complex anion is formed. Alternatively, replacement of a halide ion with the desired anion is possible. This can be done by adding a metal salt with precipitation of the metal halide formed, via an ion exchanger or by displacement of the halide ion by a strong acid (with liberation of the hydrogen halide acid). Suitable methods are, for example, in Angew. Chem. 2000, 12, pp. 3926-3945 and the literature cited therein.

Suitable alkyl radicals with which the nitrogen atom in the amines or nitrogen heterocycles can be quaternized, for example, are C 1 -C 6 -alkyl, preferably C 1 -C 10 -alkyl, particularly preferably C 1 -C 6 -alkyl and very particularly preferably methyl. The alkyl group may be unsubstituted or have one or more identical or different substituents.

Preference is given to those compounds which contain at least one five- to six-membered heterocycle, in particular a five-membered heterocycle, which has at least one nitrogen atom and, if appropriate, an oxygen or sulfur atom. Particular preference is given to those compounds which have at least one five- to five-membered heterocycle contain six-membered heterocycle having one, two or three nitrogen atoms and a sulfur or an oxygen atom, most preferably those having two nitrogen atoms. Further preferred are aromatic heterocycles.

Particularly preferred compounds are those which have a molecular weight below 1000 g / mol, very particularly preferably below 500 g / mol.

Furthermore, preference is given to those cations which are selected from the compounds of the formulas (IVa) to (IVx3)

(IVa) (IVb) (IVc)

20

(IVx1) (IVx2) (IVx3)

and oligomers containing these structures. Further suitable cations are compounds of the general formula (IVy) and (IVz)

R ² R ²

3 ^{1 +} 1 ^{1 +} 1

R-P-R S-R

I i

R R

(IVy) (IVz) and oligomers containing this structure. the above-mentioned formulas (IVa) to (IVz)

the radical R is hydrogen, a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or aliphatic, unsubstituted or by 1 to 5 heteroatoms

or suitable functional groups are interrupted or substituted radicals having 1 to 20 carbon atoms; and the radicals R ¹ to R ⁹ independently of one another represent hydrogen, a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or by 1 to 5 heteroatoms or suitable functional groups interrupted or substituted radical having 1 to 20 carbon atoms, wherein the radicals R ¹ to R ⁹ , which in the abovementioned formulas (IV) are bonded to a carbon atom (and not to a heteroatom), additionally represent halogen or a functional group can; or

two adjacent radicals from the series R ¹ to R ⁹ together also represent a bivalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or by 1 to 5 heteroatoms or suitable functional groups interrupted or substituted radical having 1 to 30 carbon atoms. As heteroatoms, in the definition of the radicals R and R ¹ to R ^{9, in} principle all heteroatoms in question which are capable of formally a -CH 2 -, a -CH =, an -O or a = C = group to replace. When the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable. Particular preferred groups are -O-, -S-, -SO-, -SO2-, -NR'-, -N =, -PR'-, -PR'2 and -SiR'2- mentioned, wherein it is R 'is the remainder of the carbon-containing residue. The radicals R ¹ to R ⁹ are, in the cases in which those in the above formulas (IV) to a carbon atom (and not to a heteroatom) bound also be bound directly via the heteroatom.

Suitable functional groups are in principle all functional groups which may be bonded to a carbon atom or a heteroatom. Suitable examples are - NR2 ', and -CN (cyano) called. Functional groups and heteroatoms may also be directly adjacent, so that combinations of several adjacent atoms, such as - O- (ether), -S- (thioether), -COO- (ester), or -CONR'- (tertiary amide ), are included, for example, di (Ci-C4-alkyl) amino, Ci-C4-alkyloxycarbonyl or Ci-C4-alkyloxy. The radicals R 'are the remaining part of the carbon-containing radical.

Preferred halogens are fluorine, chlorine, bromine and iodine.

Preferably, the radical R is for

unbranched or branched, unsubstituted or one to several times with halogen, phenyl, cyano, substituted Ci-Cis-alkyl having a total of 1 to 20 carbon atoms, such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2 Butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3 Methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl 1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3 pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2, 3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, benzyl, 3-phenylpropyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, trifluoromethyl, difluoromethyl, Fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl and undecylfluoroisopentyl;

Glycols, butylene glycols and their oligomers having 1 to 100 units and a d-Ce- alkyl as an end group, such as R ^A 0- (CHR ^B -CH ₂ -O) _n -CHR ^B -CH ₂ - or

R ^A 0- (CH ₂ CH ₂ CH ₂ CH ₂ O) n -CH ₂ CH ₂ CH ₂ CH ₂ O- with R ^A and R ^B preferably methyl or ethyl and n preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6-Dio xaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9, 12-tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl;

Vinyl; 1-propen-1-yl, 1-propen-2-yl and 1-propen-3-yl; and

N, N-di-C 1 -C 6 -alkyl-amino, such as Ν, Ν-dimethylamino and N, N-diethylamino.

The radical R particularly preferably represents unbranched and unsubstituted C 1 -C 18 -alkyl, such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-decyl, 1- dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, especially for methyl, ethyl, 1-butyl and 1-octyl, and for CH ₃ 0- (CH ₂ CH ₂ O) n -CH ₂ CH ₂ - and CH ₂ CH ₂ CH ₂ CH ₂ CN-n-CHzCHz - With n is 0 to 3. Preferably, the radicals R ¹ to R ^{9 are} independently

Hydrogen;

Halogen;

a suitable functional group;

optionally interrupted by suitable functional groups, aryl, alkyl, aryloxy, alkyl-oxy, halogen, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups Ci-cis-alkyl;

optionally interrupted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups C2-cis-alkenyl;

optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyl-oxy, halogen, heteroatoms and / or heterocycles substituted C6-Ci2-aryl;

optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyl-oxy, halogen, heteroatoms and / or heterocycles substituted C5-Ci2-cyclo-alkyl;

optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyl-oxy, halogen, heteroatoms and / or heterocycles substituted C5-Ci ₂ -cycloalkenyl; or an optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five- to six-membered, oxygen, nitrogen and / or sulfur atoms having heterocycle; or two adjacent radicals together with the atoms to which they are attached, for

an unsaturated, saturated or aromatic, optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or Hete rozyklen and optionally substituted by one or more oxygen and / or

Sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted ring.

Optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogens, heteroatoms and / or heterocycles Ci-cis-alkyl is preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl , 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2- propyl (tert -butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2- butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2- Methyl 2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2, 3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethyl-pentyl, 1,1,3,3-tetramethylbutyl, 1 -nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tridecyl, 1-tetradecyl, 1 Pentadecyl, 1-hexadecyl, 1-heptadecyl, 1-octadecyl, cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentylpropyl, cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, benzyl (phenylmethyl), diphenylmethyl (benzhydryl), triphenylmethyl, 1-phenylethyl,

2-phenylethyl, 3-phenylpropyl, α, α-dimethylbenzyl, p-tolylmethyl, 1- (p-butylphenyl) -ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p -methoxybenzyl, m-ethoxybenzyl, 2- Cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1, 2-di- (methoxycarbonyl) -ethyl, methoxy, ethoxy, 1,3-dioxolan-2-yl, 1, 3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3 Dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-phenoxyethyl, 2-phenoxypropyl,

3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxy-propyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl propyl,

4- ethoxybutyl, 6-ethoxyhexyl, C _n F2 _(s -a) + (ib) H2a + b where n is 1 to 30, 0 <a <n and b = 0 or 1 (for example CF _3, C ₂ F ₅ , CH ₂ CH ₂ -C (n- ₂ ) F _{2 (n} - ₂ ) ₊ i, C ₆ Fi ₃ , C ₈ Fi ₇ , Ci ₀ F ₂ i, Ci ₂ F ₂₅ ), chloromethyl, 2-chloroethyl, Trichloromethyl, 1, 1-dimethyl-2-chloroethyl, methoxymethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 2-isopropoxyethyl, 2-butoxy-propyl, 2-octyloxyethyl, 2-methoxy-isopropyl,

2- (methoxycarbonyl) -methyl, 2- (ethoxycarbonyl) -methyl, 2- (n-butoxycarbonyl) -methyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxo-octyl, 1-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 1-methoxy-4,8-dioxa-undecyl, 15-Methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy-5-oxa-nonyl, 14-methoxy-5,10-dioxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8- Ethoxy-3,6-dioxo-octyl, 1-ethoxy-3,6,9-trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, 1-ethoxy-4,8-dioxa-undecyl, 15- Ethoxy-4,8,12-trioxa-pentadecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy-5,10-oxa-tetradecyl.

When optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyl-oxy, halogen, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C _2- Cis-alkenyl is preferably vinyl, 2-propenyl,

3-butenyl, cis-2-butenyl, trans-2-butenyl or C _n F ₂ ( _n ) - (ib) H _2a -b with n <30, 0 <a <n and b = 0 or 1.

May optionally be substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyl-oxy, halogen, heteroatoms and / or heterocycles substituted _C6-Ci2 aryl it is preferably phenyl, tolyl, xylyl, a-naphthyl, ß-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, Diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2 , 6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl , Ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl or C6F (5- _a ) H _a with 0 <a <5.

C 5 -C 12 -cycloalkyl which is optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyl-oxy, halogen, heteroatoms and / or heterocycles is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl , Methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl,

C _n F2 ( _n ) - (ib) H2a-b with n <30, 0 <a <n and b = 0 or 1 and a saturated or unsaturated bicyclic system such. Norbornyl or norbornenyl.

Optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyl-oxy, halogen, heteroatoms and / or heterocycles C5-Ci2-cycloalkenyl is preferably 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2.5 -Cyclohexadienyl or C _n F _{2 (n} -a) -3 (ib) H _2a -3b with n <30, 0 <a <n and b = 0 or 1.

An optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle is preferably furyl, thiophenyl , Pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxy, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.

Two adjacent radicals together form an unsaturated, saturated or aromatic, optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally substituted by one or more oxygen and / or sulfur atoms and / or or one or more substituted or unsubstituted imino groups interrupted ring, it is preferably 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 2-oxa-1, 3-propylene, 1 -Oxa-1,3-propylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propenylene, 3-oxa-1, 5-pentylene, 1-aza-1,3-propenylene, 1 -d-C4-alkyl-1 -aza-1, 3-propenylene, 1, 4-buta-1, 3-dienylene, 1-aza-1, 4-buta-1, 3-dienylene or 2-aza -1, 4-buta-1,3-dienylene.

If the abovementioned radicals contain oxygen and / or sulfur atoms and / or substituted or unsubstituted imino groups, the number of oxygen and / or sulfur atoms and / or imino groups is not limited. As a rule, it is not more than 5 in the radical, preferably not more than 4, and very particularly preferably not more than 3. If the abovementioned radicals contain heteroatoms, then between two heteroatoms there are generally at least one carbon atom, preferably at least two carbon atoms.

Particularly preferably, the radicals R ¹ to R ⁹ are each independently

Hydrogen;

unbranched or branched, unsubstituted or mono- to polysubstituted by halogen, phenyl, cyano, Ci-C6-alkoxycarbonyl and / or substituted Ci-Cis-alkyl having a total of 1 to 20 carbon atoms, such as methyl, ethyl, 1-propyl, 2-propyl , 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl 1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3 Hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2- Ethyl 1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, benzyl, 3-phenyl-propyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxy-carbonyl) -ethyl, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, hepafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl and undecylfluoroporopentyl;

Glycols, butylene glycols and their oligomers having 1 to 100 units and a C 1 - to C 1 -alkyl end group, such as, for example, R ^A 0- (CHR ^B -CH ₂ -O) _n -CHR ^B -CH ₂ - or R ^A 0- (CH ₂ CH ₂ CH ₂ CH ₂ O) n-CH ₂ CH ₂ CH ₂ CH ₂ O- with R ^A and R ^{B is} preferably methyl or ethyl and n is preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3 , 6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9, 12-tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl;

Vinyl;

1-propene-1yl, 1-propen-2-yl and 1-propen-3yl; and

N, N-di-C 1 -C 6 -alkyl-amino, such as Ν, Ν-dimethylamino and N, N-diethylamino, wherein when IIIW is III, then R ^{3 is} not hydrogen.

Most preferably, the radicals R ¹ to R ⁹ independently of one another are hydrogen or C 1 -C 6 -alkyl, such as, for example, methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, phenyl , for 2-cyanoethyl, for 2- (methoxycarbonyl) ethyl, for 2- (ethoxycarbonyl) ethyl, for 2- (n-butoxycarbonyl) ethyl, for Ν, Ν-dimethylamino, for Ν, Ν-diethylamino, for chlorine and for CH ₃ O- (CH ₂ CH ₂ O) n -CH ₂ CH ₂ - and CH ₃ CH ₂ O- (CH ₂ CH ₂ O) n -CH ₂ CH ₂ - where n is 0 to 3, where when IIIw is III then R ^{3 is} not hydrogen ,

Very particularly preferred pyridinium ions (IVa) are those in which

one of R ¹ to R ^{5 is} methyl, ethyl or chlorine and the remaining R ¹ to R ^{5 are} hydrogen; R ^{3 is} dimethylamino and the remaining radicals R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen; all radicals R ¹ to R ^{5 are} hydrogen;

R ¹ and R ² or R ² and R ^{3 is} 1, 4-buta-1, 3-dienylene and the remaining R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen; and in particular those in which

R ¹ to R ^{5 are} hydrogen; or

one of the radicals R ¹ to R ^{5 is} methyl or ethyl and the remaining radicals R ¹ to R ^{5 are} hydrogen.

As very particularly preferred pyridinium ions (IVa) may be mentioned 1-methylpyridini um, 1 - ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1 (1-Hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-dodecyl) pyridinium, 1- (1-tetradecyl) pyridinium, 1- (1-hexadecyl) pyridinium , 1, 2-Dimethylpyridinium, 1-ethyl-2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2 -methylpyridinium, 1- (1-dodecyl) -2-methylpyridinium, 1- (1-tetradecyl) -2-methylpyridinium, 1- (1-hexadecyl) -2-methylpyridinium, 1-methyl-2-ethylpyridinium, 1, 2 -Diethylpyridinium, 1- (1-butyl) -2-ethylpyridinium, 1- (1-hexyl) -2-ethylpyridinium, 1- (1-octyl) -2-ethylpyridinium, 1- (1-dodecyl) -2-ethylpyridinium , 1- (1-Tetradecyl) -2-ethylpyridinium, 1- (1-hexadecyl) -2-ethylpyridinium, 1, 2-dimethyl-5-ethylpyridinium, 1, 5-diethyl-2-methyl pyridinium, 1- (1-butyl) -2-methyl-3-ethyl-pyridinium, 1- (1-hexyl) -2-methyl-3-ethylpyridinium and 1- (1 Octyl) -2-methyl-3-ethyl-pyridinium, 1- (1-dodecyl) -2-methyl-3-ethyl-pyridinium, 1- (1-tetradecyl) -2-methyl-3-ethylpyridinium and 1- (1-hexa-decyl) -2-methyl-3-ethyl-pyridinium. Very particularly preferred pyridazinium ions (IVb) are those in which

R ¹ to R ^{4 are} hydrogen; or

one of the radicals R ¹ to R ^{4 is} methyl or ethyl and the remaining radicals R ¹ to R ^{4 are} hydrogen.

Very particularly preferred pyrimidinium ions (IVc) are those in which - R ^{1 is} hydrogen, methyl or ethyl and R ² to R ^4, independently of one another, are hydrogen or methyl; or

R ^{1 is} hydrogen, methyl or ethyl, R ² and R ^{4 are} methyl and R ^{3 is} hydrogen.

Very particularly preferred pyrazinium ions (IVd) are those in which

R ^{1 is} hydrogen, methyl or ethyl and R ² to R ^{4 are} independently hydrogen or methyl;

R ^{1 is} hydrogen, methyl or ethyl, R ² and R ^{4 are} methyl and R ^{3 is} hydrogen;

R ¹ to R ^{4 are} methyl; or

R ¹ to R ^{4 are} hydrogen. Very particular preference is given to using as imidazolium ions (IVe) those in which

R ^{1 is} hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl or 2-cyanoethyl and R ² to R ^{4 are} independently hydrogen, methyl or ethyl. Particularly preferred imidazolium ions (IVe) which may be mentioned are 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-Tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-Butyl) -3-ethylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) -3-ethylimidazolium, 1- (1-hexyl) -3- butyl imidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-octyl) -3-ethylimidazolium, 1- (1-octyl) -3-butylimidazolium, 1- (1-dodecyl) -3- methylimidazolium, 1- (1-dodecyl) -3-ethylimidazolium, 1- (1-dodecyl) -3-butylimidazolium, 1- (1-dodecyl) -3-octylimidazolium, 1- (1-tetradecyl) - 3-methylimidazolium, 1- (1-tetradecyl) -3-ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-tetradecyl) -3-octylimidazolium, 1- (1-hexadecyl ) -3-methylimidazolium, 1- (1-hexadecyl) -3-ethylimidazolium, 1- (1-hexadecyl) -3-butylimidazolium, 1- (1-He xadecyl) -3-octylimidazolium, 1, 2-dimethylimidazolium, 1, 2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- ( 1-hexyl) -2,3-dimethyl-imidazolium, 1- (1-octyl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl 3-ethylimidazolium, 3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1, 4,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1, 4,5-trimethyl-3 ethylimidazolium, 1, 4,5-trimethyl-3-butylimidazolium, 1, 4,5-trimethyl-3-octylimidazolium and 1 - (prop-1 -en-3-yl) -3-methylimidazolium.

The most preferred 1,3-dialkylimidazolium ions are 1-butyl-3-methylimidazolium ion and 1-ethyl-3-methylimidazolium ion.

Very particular preference is given as Pyrazoliumionen (IVf), (IVg) or (IVg ') such, in which

R ^{1 is} hydrogen, methyl or ethyl and R ² to R ^{4 are} independently hydrogen or methyl.

Very particularly preferred pyrazolium ions (IVh) are those in which

R ¹ to R ^{4 are} independently hydrogen or methyl.

Very particular preference is given to using 1-pyrazolinium ions (IVi) as those in which

independently of one another R ¹ to R ^{6 are} hydrogen or methyl. Very particular preference is given to using 2-pyrazolinium ions (IVj) or (IVj ') as those in which

R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² to R ^{6 are} independently hydrogen or methyl.

Very particular preference is given to using as 3-pyrazolinium ions (IVk) or (IVk ') those in which R ¹ and R ^{2 are} independently hydrogen, methyl, ethyl or phenyl and R ³ to R ^{6 are} independently hydrogen or methyl.

Very particularly preferred as Imidazoliniumionen (IVI) are those in which

R ¹ and R ^{2 are} independently hydrogen, methyl, ethyl, 1-butyl or phenyl, R ³ and R ^{4 are} independently hydrogen, methyl or ethyl, and R ⁵ and R ^{6 are} independently hydrogen or methyl.

Very particular preference is given to imidazolinium ions (IVm) or (IVm ') those in which

R ¹ and R ^{2 are} independently hydrogen, methyl or ethyl and R ³ to R ⁶ are independently hydrogen or methyl.

Very particular preference is given to using as imidazolinium ions (IVn) or (IVn ') those in which

R ¹ to R ^{3 are} independently hydrogen, methyl or ethyl and R ⁴ to R ^{6 are} independently hydrogen or methyl.

Very particular preference is given as Thiazoliumionen (IVo) or

(IVo ') and as Oxazoliumionen (IVp) such a, in which

R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² and R ^{3 are} independently hydrogen or methyl.

Very particular preference is given to using as 1,2,4-triazolium ions (IVq), (IVq ') or (IVq ") those in which

R ¹ and R ^{2 are} independently hydrogen, methyl, ethyl or phenyl and R ^{3 is} hydrogen, methyl or phenyl.

Very particular preference is given to using as 1,3,3-triazolium ions (IVr), (IVr ') or (IVr ") those in which

- R ^{1 is} hydrogen, methyl or ethyl and R ² and R ^{3 are} independently hydrogen or methyl, or R ² and R ³ together are 1, 4-buta-1, 3-dienylene.

Very particularly preferred pyrrolidinium ions (IVs) are those in which

R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² to R ^{9 are} independently hydrogen or methyl.

Very particular preference is given to using as imidazolidinium ions (IVt) those in which

R ¹ and R ^{4 are} independently hydrogen, methyl, ethyl or phenyl and R ² and R ³ and R ⁵ to R ^{8 are} independently hydrogen or methyl.

Very particular preference is given to using as ammonium ions (IVu) those in which

R ¹ to R ^{3 are} independently of each other Cr to Cie alkyl; or

- R ¹ and R ² together are 1, 5-pentylene or 3-oxa-1, 5-pentylene and R ^{3 is} Ci-Ci ₈ alkyl or 2-cyanoethyl.

As very particularly preferred ammonium ions from the group (IVu) may be mentioned methyl tri (1-butyl) -ammonium and tetra (1-butyl) -ammonium; from the group (IVx1) N, N-dimethylpiperidinium and 1-butyl-1-methylpiperidinium; from the group (IVx2) 1-ethyl-3-methylimidazoinium; and from the group IVx3 N, N-dimethylmorpholinium. Examples of the tertiary amines from which the quaternary ammonium ions of the general formula (IVu) are derived by quaternization with the abovementioned radicals R are diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethyl hexylamine, diethyloctylamine, diethyl (2-ethylhexyl) amine, di-n-propylbutylamine, di-n-propyl-n-pentylamine, di-n-propylhexylamine, di-n-propyloctylamine, di-n-propylamine (2-ethylhexyl) amine, di-isopropylethylamine, di-isopropyl-n-propylamine, di-isopropyl-butylamine, diisopropylpentylamine, di-iso-propylhexylamine, di-isopropyloctylamine, diisobutylamine. propyl- (2-ethylhexyl) -amine, di-n-butylethylamine, di-n-butyl-n-propylamine, di-n-butyl-n-pentylamine, di-n-butylhexylamine, di-n-butyloctylamine, di-n-butyl-n-pentylamine n-butyl- (2-ethylhexyl) -amine, Nn-butylpyrrolidine, N-sec-butylpyrrodidine, N-tert-butylpyrrolidine, Nn-pentylpyrrolidine, N, N-dimethylcyclohexylamine, Ν, Ν-diethylcyclohexylamine, N, N-di-n-butylcyclohexylamine, Nn-propylpiperidine, N-isopropylpiperidine, Nn-butyl piperidine, N-sec-butylpiperidine, N-tert-butylpiperidine, Nn-pentylpiperidine, Nn-butylmorpholine, N-sec-butylmorpholine, N-tert-butylmorpholine, Nn-pentylmorpholine, N-benzyl-N-ethylaniline, N- Benzyl-Nn-propylaniline, N-benzyl-N-iso-propylaniline, N-benzyl-Nn-butylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-di- n-butyl-p-toluidine, diethylbenzylamine, di-n-propylbenzylamine, di-n-butylbenzylamine, diethylphenylamine, di-n-propylphenylamine and di-n-butyl-phenylamine.

Preferred quaternary ammonium salts of the general formula (IVu) are those which can be derived from the following tertiary amines by quaternization with the abovementioned radicals R, such as diisopropylethylamine, diethyl-tert-butylamine, di-iso-propylbutylamine , Di-n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines of pentyl isomers.

Particularly preferred tertiary amines are di-n-butyl-n-pentylamine and tertiary amines of pentyl isomers. Another preferred tertiary amine having three identical moieties is tri allylamine.

Very particular preference is given to using as guanidinium ions (IVv) those in which

the nitrogen atoms are present in ring structures; or

R ¹ to R ^{5 are} methyl.

An especially preferred guanidinium ion (IVv) is N, N, N ', N', N ", N" -hexamethylguanidinium.

Very particular preference is given to using as cholinium ions (IVw) those in which

R ¹ and R ^{2 are} independently methyl, ethyl, 1-butyl or 1-octyl and R ^{3 is} methyl or ethyl, ₂ ;

R ^{1 is} methyl, ethyl, 1-butyl or 1-octyl, R ^{2 is} -CH ₂ -CH ₂ -OR ⁴ - and R ³ and R ^{4 are} independently methyl or ethyl; or

R ^{1 is} a -CH ₂ -CH ₂ -OR ⁴ group, R ^{2 is} a -CH ₂ -CH ₂ -OR ⁵ group and R ³ to R ^{5 are} independently methyl or ethyl. Particularly preferred cholinium ions (IVw) are those in which R ^{3 is} selected from methyl, ethyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 1 1 -methoxy-3,6 , 9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 1-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9- Methoxy-5-oxa-nonyl, 14-methoxy-5,10-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 1-ethoxy-3,6 , 9-trioxa undecyl, 7-ethoxy-4-oxa-heptyl, 1-ethoxy-4,8-dioxa-decyl, 15-ethoxy-4,8,12-trioxa-pentadecyl, 9-ethoxy 5-oxa-nonyl or 14-ethoxy-5,10-oxa-tetra-decyl.

Very particular preference is given to using as amidinium ions (IVx) those in which the nitrogen atoms are present in a ring structure.

As very particularly preferred amidinium ions (IVx) may be mentioned a simply protonated form of 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) or of 1, 5-diazabicyclo [4.3.0] non-5-ene ,

Very particularly preferred as phosphonium ions (IVy) are those in which

R ¹ to R ³ independently of one another are C 1 -C 6 -alkyl, in particular butyl, isobutyl, 1-hexyl or 1-octyl.

Among the heterocyclic cations mentioned above, the pyridinium ions, pyrazolinium, pyrazolium ions and the imidazolinium and imidazolium ions are preferred. Furthermore, ammonium ions are preferred.

Particularly preferred are 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-hexyl) -pyridinium, 1 - (1-octyl) -pyridinium, 1- (1-dodecyl) -pyridinium, 1- (1-tetradecyl) -pyridinium, 1- (1-hexadecyl) -pyridinium, 1, 2-dimethylpyridinium, 1-ethyl 2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1- (1- Do-decyl) -2-methylpyridinium, 1- (1-tetradecyl) -2-methylpyridinium, 1- (1-hexadecyl) -2-methylpyridinium, 1-methyl-2-ethylpyridinium, 1, 2-diethylpyridinium, 1- (1-Butyl) -2-ethylpyridinium, 1- (1-hexyl) -2-ethylpyridinium, 1- (1-octyl) -2-ethylpyridinium, 1- (1-dodecyl) -2- ethylpyridinium, 1- (1-tetradecyl) -2-ethylpyridinium, 1- (1-hexadecyl) -2-ethylpyridinium-um, 1, 2-dimethyl-5-ethylpyridinium, 1, 5-diethyl-2-methyl- pyridinium, 1- (1-butyl) -2-methyl-3-ethylpyridinium, 1- (1-hexyl) -2-methyl-3-ethylpyridinium, 1- (1-octyl) -2-methyl- 3-ethyl-pyridinium m, 1- (1-dodecyl) -2-methyl-3-ethylpyridinium, 1- (1-tetradecyl) -2-methyl-3-ethyl-pyridinium, 1- (1-hexadecyl) -2- Methyl 3-ethyl-pyridinium, 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1 - (1-tetradecyl) imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1 -Hexyl) -3-methylimidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- ( 1-hexadecyl) -3-methylimidazolium, 1, 2-dimethylimidazolium, 1, 2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium , 1- (1-hexyl) -2,3-dimethylimidazolium and 1- (1-octyl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylol ethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1,1,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,4. 5-trimethyl-3-ethylimidazolium, 1, 4,5-trimethyl-3-butylimidazolium, 1, 4,5-trimethyl-3-octylimidazolium and 1- (prop-1-en-3-yl) -3-metyl- imidazolium.

As anions, in principle, all anions can be used.

The anion [Y] ⁿ - of the ionic liquid is preferably selected from

the group of halides

the group of carboxylic acids of the general formula:

RCOO ¹ - the group of carbonates and carbonic esters of the general formula:

HCOs ¹ -, COs ^{2 "} , RCOs ¹ - the group of polybasic carboxylic acids of the general formula:

R (COOH) n (COO) _m (n> 0, m> 0)

the group of aromatic hydroxyl compounds of the general formula:

R _m C ₆ H _n (OH) p (0-) _q (m + n + p + q = 6, q> 0).

Therein R Ci-C3o-alkyl, optionally interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted imino interrupted C2-Ci ₈ alkyl, C6-Ci4-aryl, C5-Ci2-cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle, two of them together having one unsaturated, saturated or aromatic, optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more unsubstituted ierte or substituted imino groups can form interrupted ring, said radicals may each be additionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles.

These are optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or heterocycles substituted Ci-Cis-alkyl, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl , Pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethylbutyl, 1, 1, 3, 3 Tetramethylbutyl, benzyl, 1-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl , m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxy-carbonylpropyl, 1, 2-di- (methoxycarbonyl) -ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2 -Bu-toxyethyl, diethoxymethyl, diethoxyethyl, 1, 3-dioxolan-2-yl, 1, 3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3 dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, trichloromethyl, Tr ifluoromethyl, 1, 1-dimethyl-2-chloroethyl, 2-methoxy-isopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthio-ethyl, 2,2,2-trifluoroethyl, 2-dimethylaminoethyl, 2- Dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenylene oxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl.

Optionally interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C2-Ci8-alkyl are, for example, 5-methoxy-3-oxapentyl, 8-methoxy-3,6- dioxo-octyl, 1 1-methoxy-3,6,9-trioxaundecyl, 7-methoxy-4-oxaheptyl, 1-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxapentadecyl, 9-methoxy-5-oxano-nyl, 14-methoxy-5,10-oxatetradecyl, 5-ethoxy-3-oxapentyl, 8-ethoxy-3,6-dioxo-octyl, 1-ethoxy-3,6,9 trioxaundecyl, 7-ethoxy-4-oxaheptyl, 1-ethoxy-4,8-dioxaundecyl, 15-ethoxy-4,8,12-trioxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5,10- oxatetra-decyl.

The number of non-adjacent oxygen and / or sulfur atoms and / or imino groups is basically not limited, or is automatically limited by the size of the remainder or of the ring building block. As a rule, it is not more than 5 in the respective radical, preferably not more than 4 or very particularly preferably not more than 3. Furthermore, at least one, preferably at least two, carbon atoms (e) are generally present between two heteroatoms.

Substituted and unsubstituted imino groups may be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino.

The term "functional groups" is to be understood as meaning, for example, the following: di- (C 1 -C 4 -alkyl) amino, C 1 -C 4 -alkyloxycarbonyl, cyano or C 1 -C 4 -alkoxy where C 1 -C 4 -alkyl is methyl, ethyl , Propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

Optionally C6-C4-aryl substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles are, for example, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl , Dichloro-phenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl , 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6 -Dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl.

Optionally C5-C12-cycloalkyl which is substituted by suitable functional groups, aryl, alkyl, aryloxy, halogen, heteroatoms and / or heterocycles are, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclo- hexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.

A five- to six-membered heterocycle having oxygen, nitrogen and / or sulfur atoms is, for example, furyl, thiophenyl, pyryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyryl, Me - Thoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, iso-propylthiophenyl or tert-butylthiophenyl.

Particularly preferred anions in the ionic liquids are the halides, more preferably chloride, bromide and iodide, and most preferably chloride.

The catalyst is preferably selected from the group consisting of 1-ethyl-3-methylimidazolium bromide (EMIM-Br), 1-ethyl-3-methylimidazolium chloride (EMIM-CI), 1-ethyl-3-methylimidazolium dicyanodiamide (EMIM-DICY ), 1-ethyl-3-methylimidazolium iodide (EMIM-I), 1-ethyl-2,3-methylimidazolium bromide (EDMIM-Br), 1-ethyl-3-methylimidazolium diethyl phosphate, (EMIM-DEP), 1 Benzyl-3-methylimidazolium chloride (BEMIM-CI), 1-butyl-1-methylpiperidinium chloride (BMPM-CI), 1- (2-hydroxyethyl) -3-methylimidazolium chloride (HEMIM-CI). The catalyst is particularly preferably selected from the group 1-ethyl-3-methylimidazolium bromide (EMIM-Br), 1-benzyl-3-methylimidazolium chloride (BEMIM-CI), 1-butyl-1-methylpiperidinium chloride ( BMPM-CI), 1-butyl-3-methylpiperidinium chloride (BMPM-CI), 1- (2-hydroxyethyl) -3-methylimidazolium chloride (HEMIM-CI). In a further preferred embodiment, at least two of these catalysts are used.

In a further preferred embodiment, the ionic liquid is a combination of Lewis acid and a Lewis base, these being preferably selected from one of the abovementioned preferences. Co-catalysts:

In other preferred embodiments, urea derivatives are used as co-catalyst in addition to the above-mentioned catalyst.

The use of ureas as co-catalysts helps in the reaction of the isocyanate with the epoxide. A faster reaction of the isocyanate is advantageous because longer residence times of the isocyanate in the reaction mixture increase the likelihood of trimerization of the isocyanate and thus worsen the chemoselectivity for oxazolidone formation. Preferred are ureas, which do not split off primary amines upon decomposition, for example when heat is applied. Suitable co-catalysts are therefore urea derivatives of the following formula

in which

R1, R2, R3 and R4 are alkyl radicals having independently of one another 1 to 10 carbon atoms or

R 1 and R 2 are alkyl radicals having independently of one another 1 to 10 carbon atoms and R 3 is an aryl radical and at the same time R 4 is a hydrogen atom or R 3 is an aryl radical and R 4 is a hydrogen atom.

The aryl radical is substituted in a preferred embodiment, preferably with a further urea-scaffold. In other preferred embodiments, the aryl moiety is substituted with multiple urea moieties. The corresponding structures are also addressed as polyurea.

In other preferred embodiments, the alkyl substituents are linked together and have ring structures. Preferred examples of this are 1, 3-dimethyl-3,4,5,6-tetrahydro-2 (1 H) -pyrimidinone and 1, 3-dimethyl-2-imidazolidinone. Particularly preferred are co-catalysts selected from the group 3,3 '- (4-methyl-1, 3-phenylene) bis (1, 1-dimethylurea) and 1, 1-dimethyl-3-phenylurea. Commercially available products of this class are e.g. the dimethylureas from AlzChem, trade name Dyhard.

Polymer production:

The diepoxide, the diisocyanate and the catalyst are used according to the enumeration and preferences given above.

In a first step, the epoxide and the catalyst are dissolved in a solvent and heated to reaction temperature. The reaction temperature is preferably in a range of from 140 ° C to 220 ° C, more preferably from 150 ° C to 200 ° C, and particularly preferably from 160 ° C to 180 ° C.

The solution is rendered inert with nitrogen, oxygen must be excluded in the reaction. Then the isocyanate is added slowly while maintaining the reaction temperature. The content of free isocyanate in the reaction mixture should be kept as low as possible to prevent trimerization of the isocyanate. This is controlled either by the rate of metered addition of the isocyanate and / or the reactivity, that is the amount of added catalyst.

In a preferred embodiment, the water content of the reaction mixture is less than 0.1 wt .-%. In particular, the side reaction of the isocyanate to urea is prevented. The molar ratio of the diepoxide to the diisocyanate is in a range between 1, 0: 0.5 to 0.5: 1, 0, preferably between 1, 0: 0.9 to 0.9: 1, 0 and particularly preferably 1, 0: 1, 0.

The catalyst concentration is 0.05 mol% to 5 mol% based on epoxide groups, preferably 0.05 mol% to 2 mol%, and particularly preferably 0.05 mol% to 0.5 mol%.

The concentration of the co-catalyst is 0.01 mol% to 1000 mol% based on epoxide groups of the diepoxide, preferably 0.05 mol% to 100 mol%, particularly preferably 0.05 mol% to 10 mol% and in particular 0.05 mol% to 1 mol%.

In a preferred embodiment, the co-catalyst is used as solvent for the reactants, wherein in a preferred embodiment, the co-catalyst is 1, 3-dimethyl-2-imidazolidone.

The solvents are preferably dried before use. In a preferred embodiment, the drying is carried out by a molecular sieve.

Suitable solvents are aprotic-polar, in order not to react with the isocyanate, preferably dichlorobenzene, preferably 1, 2, dichlorobenzene, 1, 2, 3; 1, 2, 4 and 1, 3,5 trichlorobenzene, sulfonane, mesitylene, or N-methylpyrolidone. A particularly suitable solvent is sulfolane (tetrahydrothiophene-1, 1-dioxide).

In another preferred embodiment, the catalyst, in a further preferred together with the co-catalyst, in the solvent A and then heated to reaction temperature. The solvent containing the catalyst, in the preferred embodiment the catalyst and the co-catalyst, is also referred to as mixture A.

Mixture A is deoxygenated, ie rendered inert, as oxygen adversely affects the reaction. In a preferred embodiment, this inertization is carried out with nitrogen. Then the isocyanate is mixed homogeneously with the diepoxide in a solvent B, which is also referred to as mixture B, while slowly adding the reaction temperature to the mixture A containing the catalyst, preferably the catalyst and the co-catalyst. The mixture of mixture A and mixture B is the reaction mixture. In another preferred embodiment, the co-catalyst is contained in the mixture B. In a further preferred embodiment, the epoxide and the catalyst are presented, then heated to reaction temperature and then the isocyanate added. The isocyanate is added continuously or batchwise, ie in portions. In this method, preferably, little or no solvent is used. As a result, the melt viscosities can be very high, which is why particularly suitable agitators must be used. Preferred examples of such stirrers are extruders or Plasti-Corder, such as those offered by the company. Brabender.

In the processes mentioned, it is important to keep the content of free isocyanate in the reaction mixture as low as possible in order to prevent the trimerization of the isocyanate. This is controlled by at least one of the following: the rate of metered addition of the mixture B, the reactivity of the catalyst, the reactivity of the co-catalyst, the amount of catalyst added, the amount of co-catalyst and / or the reaction temperature. Preferably, the said processes are carried out in the absence of oxygen, since this adversely affects the reaction.

The reaction temperature of the processes is preferably in a range of 140 ° C to 220 ° C, more preferably 150 ° C to 200 ° C, and particularly preferably 160 ° C to 180 ° C.

use

The present invention also relates to the use of a polymer according to the invention for the production of applications selected from, coating, damping element, bellows, foil, fiber, molded article, floor for building and transportation, non-woven fabric, preferably seal, roll, shoe sole, hose, cable , Connectors, cable connectors, connector parts, cable sheathing, cushions, laminate, profile, belt, saddle, foam, by additional foaming of the preparation, plug connection, towing cable, solar module, cladding in automobiles, wiring harness components, circuit carriers, circuit carrier components, three-dimensionally injection-molded circuit carriers, electrical connection elements, mechatronic components, modifiers for thermoplastic materials, ie Substance that influences the properties of another material. Each of these uses taken alone is a preferred embodiment, also referred to as an application. The polymer is preferably provided in a first step as granules or powder. The applications are preferably made by injection molding, calendering, powder sintering, or extrusion.

The moldings or semifinished products to be produced according to the invention from the thermoplastic molding compositions can be used, for example, in the automotive, electrical, electronic, telecommunications, information technology, entertainment, computer industry, in vehicles and other means of transportation, in ships, spaceships, in the household, in office equipment, Sports, in in medicine and in general in articles and building parts which require increased fire protection.

The following examples show by way of example the advantageous property of the catalysts and their use in a polymer according to the invention. The examples are in no way limiting to the inventive idea.

Examples: Starting materials:

0-Cresyl glycidyl ether (CAS No. 2210-79-9) Sigma-Aldrich

Napthyl isocyanate, (CAS No. 86-84-0), Sigma-Aldrich

Bisphenol A diglycidyl ether, (CAS # 1675-54-3), Sigma-Aldrich D 3415-250g

2,4-Toloyl diisocyanate, (2,4-TDI) (CAS # 584-84-9), Sigma-Aldrich

N, N "- (4-methyl-m-phenylene) to [N ', N'-dimethylurea] (DYHARD® UR500)

(CAS No. 17526-94-2), Alz Chem

catalysts:

1-ethyl-3-methylimidazolium dicyandiamide (EMIM-DICY, CAS No. 370865-89-) 1-ethyl-3-methylimidazolium chloride (EMIM-CI, CAS No. 65039-09-0, Basionics St 80, BASF) 7, Basionics VS 03, BASF)

1-ethyl-3-methylimidazolium ethylsulfate (EMIM-EtOS0 ₃ , CAS No. 342843-75-5, Basionics LQ 01, BASF)

1-ethyl-3-methylimidazolium bromide (EMIM-Br, CAS No. 65039-08-9, lolitec)

1-ethyl-3-methylimidazolium tosylate (EMIM-TOS, CAS No. 328090-25-1, Lolitec)

1-ethyl-3-methylimidazolium diethyl phosphate, (EMIM-DEP, CAS No. 848641-69-0, lolitec) 1-benzyl-3-methylimidazolium chloride (BEMIM-CI, CAS No. 36443-38-8, Fa lolitec)

1-butyl-1-methylpiperidinium chloride (BMPM-CI, CAS No. 845790-13-8, lolitec)

1-butyl-3-methylimidazolium chloride (BMIM-CI, CAS No. 79917-90-1, lolitec)

1- (2-hydroxyethyl) -3-methylimidazolium chloride (HEMI M-CI, CAS No. 61755-34-8, lolitec)) cocatalysts:

N, N "- (4-methyl-m-phenylene) to [N ', N'-dimethylurea] (DYHARD® UR500)

(CAS No. 17526-94-2), AlzChem

Solvent:

Sulfolane (CAS No. 126-33-0 Merck, No. 845056), dried over molecular sieve 4A (Roth, bead form)

Ν, Ν-dimethylacetamide (DMAC) (CAS No. 127-19-5 Merck, No. 803235)

1, 2-dichlorobenzene (CAS No. 95-50-1, Sigma-Aldrich)

Acetic acid (CAS No. 64-19-7 Bernd Kraft, No. 16873.4000)

Model reactions (to determine the selectivity of the catalysts): In a 50 ml three-necked flask, rendered inert with dry nitrogen, with thermocouple, magnetic stirrer, condenser, septum and N 2 purge via condenser, 8.0 g (48.72 mmol) of o-cresylglycidyl ether (CAS No. 2210-79) were added. 9, Sigma-Aldrich) and mixed with 0.24 mmol (0.5 mol%) of catalyst. The mixture was heated by means of an oil bath with stirrers to 160 ° C, while the catalyst was completely dissolved. Subsequently, 4.12 g (24.36 mmol) of naphthyl isocyanate (CAS No. 86-84-0, Sigma-Aldrich) in 5 min by syringe pump / cannula through the septum. added at a constant rate. Immediately after addition, a sample about 200-300μΙ_ of the reaction liquid was taken via syringe over the septum and recorded an IR spectrum. At intervals of 0.5 h, 1 h, and further hourly, further samples were taken and examined by IR. After complete reaction of the Isocyana- tes, recognizable by the decrease in the IR band at 2256cnr1 was stirred for a further hour at reaction temperature, then the contents of the flask was cooled with stirring to about 70 ° C and filled into a sample bottle. An epoxide titration (EEW) and a GPC analysis were carried out (solvent DMAC, reference is synthetically produced trimer of naphthyl isocyanate).

Table 1

IR R ox Tr is the IR ratio of oxazolidone to trimer (isocynaurate)

EEW = epoxy equivalent weight (epoxi-equivivalent weight) is a measure of the side reaction of epoxy homopolymerization.

The table shows that the catalysts of Examples 4, 7, 8, 9 and 10 lead to particularly good polymer properties. These are therefore preferred. Example 1 1 - Polymer reaction

In a 100 ml three-necked round bottomed flask, equipped with magnetic stirrer, condenser, thermocouple and septum, inerted with dry nitrogen, 10.0 g (28.6 mmol) of bisphenol A diglycidyl ether (CAS No. 1675-54-3, Sigma Aldrich D 3415-250 g) and 20.9 mg (0.143 mmol) of 1-ethyl-3-methylimidazolium chloride (EMIM-CI, Basionics St 80, BASF, CAS No. 65039-09-0) and weighed dissolved in 58.24 g sulfolane. The solution was heated to 160 ° C with N 2 purge. In 60 min. 4.54 g (26.1 mmol) of 2,4-TDI (CAS No. 584-84-9, Sigma-Aldrich) were metered in continuously with stirring by means of a syringe pump / cannula. After complete addition, a sample of about 200-300μΙ was taken by syringe and examined by IR. At regular intervals samples were taken, after complete reaction of Isocyana- tes, recognizable by the decrease in the IR band at 2256cm-1 was stirred for a further hour at reaction temperature, then the solution cooled to about 50 ° C and slowly submerged with vigorous stirring in 400 mL ethanol / water mixture (80/20 v / v). The polymer formed precipitated out and could be separated by vacuum filtration. The polymer was washed twice with 100 ml of ethanol and filtered through filters and then dried in a petri dish in a vacuum oven at about 50 ° C to constant mass. A white, fine powder which was clearly soluble in DMAC was obtained with the following characteristics:

Reactivity (.NCO = 0, min.): 300 min

Mn (GPC): 2591 g / mol

Tg (DSC): 178 ° C

Rox trimer (IR): 0.62

Melting range: 150-160 ° C (Kofier)

Example 12 - Polymer reaction

In a dry nitrogen nitrogenized 100 ml three-neck round bottom flask equipped with

Magnetic stirrer, condenser, thermocouple, and septum were mixed with 10.0 g (28.6 mmol) of bisphenol A diglycidyl ether (CAS No. 1675-54-3, Sigma-Aldrich D 3415-250 g), 27.3 mg (m.p. 0.143 mmol) of 1-ethyl-3-methylimidazolium bromide (EMIM-Br, Lolitec Co., CAS No. 65039-08-9) and 7.5 mg

(0.0284 mmol) N, N "- (4-methyl-m-phenylene) to [N ', N'-dimethylurea] (DYHARD® UR500, Alz Chem, CAS No. 17526-94-2) and weighed into The solution was heated under N 2 purge to 160 ° C. In the course of 60 minutes, 4.95 g (28.4 mmol) of 2,4-TDI (CAS No. 584-84 After completion of the addition, a sample was taken by syringe and examined by IR, and samples were taken at regular intervals after complete reaction of the isocyanate, recognizable by the decrease in the IR band 2256cm-1 was stirred for a further hour at reaction temperature, then the solution was cooled to about 50 ° C and slowly added with vigorous stirring to 400 ml of ethanol / water (80/20 v / v) mixture, precipitating the polymer formed It was isolated by vacuum filtration and the polymer was purified twice with 100 ml of ethanol and then in a petroleum dish in a vacuum oven cupboard dried at about 50 ° C to constant mass. A white, fine powder which was clearly soluble in DMAC was obtained with the following characteristics: Reactivity (.NCO = 0, min.): 90 min.

Mn (GPC): 6344

Tg (DSC): 179 ° C

Rox / trimer (IR): 0.69

Example 13 - Polymer reaction, preferred embodiment

In a 500 ml three-necked round-bottomed flask, rendered inert with dry nitrogen, equipped with KPG stirrer, condenser, thermocouple dropping funnel and septum, 135.9 g of sulfolane and 0.1372 g (71.5 mmol) of 1-butyl-1-methylpiperidinium chloride (BMPM) were CI, CAS No. 845790-13-8) and 0.0378 g (14.3 mmol) of N, N "- (4-methyl-m-phenylene) to [N ', N'-dimethylurea] (DYHARD® UR500, Alz Chem, CAS No. 17526-94-2) and heated to 175 ° C, thereby completely dissolving the catalysts, in a separate container, 50.0 g (0.1431 mol) of bisphenol A diglycidyl ether (CAS No. 1675-54-3) and 23.7 g (0.1359 mol) of 2,4-TDI (CAS No. 584-84-9) were mixed with 36.4 g of 1,2-dichlorobenzene and The mixture was homogenized with stirring at RT, and the mixture was transferred to the dropping funnel and metered into the catalyst solution at a constant metering rate over 90 minutes After complete addition, a sample was taken by syringe and examined by IR peak for the oxazolidone band (1750 cm-1) and no signal for free isocyanate (2256 cm-1). The reaction solution was stirred for a further hour at reaction temperature, then cooled to about 80 ° C and slowly added with vigorous stirring in 1000 ml of ethanol / water mixture (80/20 v / v). The polymer formed precipitated out and could be separated by vacuum filtration. The polymer was washed twice with 100 ml of ethanol and then dried in a petri dish in a vacuum oven at about 80 ° C to constant mass. The resulting powder was then dissolved in 200 ml of dichloromethane and precipitated again in 800 ml of ethanol. The polymer was filtered off and slurried twice with 100 ml of ethanol each time and filtered. The resulting polymer powder was then dried at 160 ° C in a vacuum oven for 4h. A white, fine powder which was clearly soluble in DMAC was obtained with the following characteristics:

Reactivity (.NCO = 0, min.): After complete addition of the solution

Mn (GPC): 1 1865

Tg (DSC): 179 ° C

Rox trimer (I R) ^ 0.71

Example 14 - Determination of Chemoselectivity of Catalyst (R):

The chemoselectivity of catalysis with respect to oxazolidone formation is evaluated by evaluating the I R signals for oxazolidone (1750 cm ^-1 ) and isocyanurate (1705 cm ^-1 ) according to the following formula:

R (ox: trimer) = peak H ·

peak H Ox + peak H trimer Example 15 - Determination of Epoxide Number (% EpO)

To characterize the content of compounds on oxirane groups ("epoxide groups"), an epoxide titration was performed, the epoxide number (% EpO) obtained indicating how many grams of oxirane oxygen are contained in 100 grams of a sample.

Crystal violet is used as an indicator. The determination presupposes the absence of water, bases and amines.

reagents:

(1) 0.1-N-perchloric acid (Merck) in glacial acetic acid

(2) Tetraethylammonium bromide (Fluka) in the form of a solution of 100 g of tetraethylammonium bromide in 400 ml of glacial acetic acid

(3) crystal violet (Merck); To prepare the indicator solution, 0.2 g of crystal violet was dissolved in 100 ml of glacial acetic acid. Execution:

0.2 to 0.5 g of the sample containing oxirane rings are placed in an Erlenmeyer flask. The sample is dissolved in 50 ml of anhydrous acetone. Add 10 ml of tetraethylammonium bromide solution (see above) and 3 drops of crystal violet solution (see above). The mixture is titrated with a 0.1N solution of perchloric acid in glacial acetic acid. The endpoint is reached as soon as the color changes from blue to green.

Before carrying out the actual titration, a blank test is carried out (this contains no oxirane compound) in order to exclude measurement errors.

Evaluation:

The epoxide content% EpO is calculated as follows:% EpO = [(a-b) +0.160] / E

a: = consumption ml of 0.1 N perchloric acid in titration

b :: = consumption ml of 0.1 N perchloric acid in blank

E: = sample weight in grams

The epoxy equivalent weight (EEW) is calculated according to the following formula:

EEW = 1600 /% Epo

The dimension of the EEW is g / eq.

The reactivity is the period of time after which a sample in IR gives no visible signal of the isocyanate band (2256 cm ^-1 )

Claims

Claims:

Thermoplastic polymer prepared from at least diisocyanate and diepoxide using a catalyst wherein the catalyst is an ionic liquid.

The polymer of claim 1, wherein the catalyst is an ionic liquid having a melting temperature below 250 ° C, preferably below 200 ° C, and more preferably below 150 ° C.

The polymer of claim 1 or 2, wherein the ionic liquid is a combination of Lewis acid and a Lewis base.

A polymer according to any one of the preceding claims wherein the ionic liquid is a salt of the following formula (I)

[A] "[ΥΓ (i),

in which n stands for 1, 2, 3 or 4,

[A] ^{+ represents} a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation, and

[Y] ⁿ - represents a mono-, di-, tri- or tetravalent anion.

Polymer according to one of the preceding claims, wherein the catalyst is selected from the group 1 -Ethyl-3-methylimidazolium bromide (EMIM-Br), 1-ethyl-3-methylimidazolium chloride (EMIM-CI), 1-ethyl-3 -methylimidazolium dicyandiamide (EMDIMICY), 1-ethyl-3-methylimidazolium iodide (EMIM-I), 1-ethyl-3-methylimidazolium diethyl phosphate, (EMIM-DEP), 1-benzyl-3-methylimidazolium chloride (BEMIM-CI ), 1-butyl-1-methylpiperidinium chloride (BMPM-CI).

Polymer according to one of the preceding claims, wherein the catalyst is selected from the group 1 -Ethyl-3-methylimidazolium bromide (EMIM-Br), 1-benzyl-3-methylimidazolium chloride (BEMIM-CI), 1-butyl-1 -methylpiperidinium chloride (BMPM-CI),, 1- (2-hydroxyethyl) -3-methylimidazolium chloride (HEMIM-CI)

Polymer according to one of the preceding claims, wherein in addition to the catalyst, a co-catalyst is used, which is preferably a urea derivative.

A polymer according to any one of the preceding claims, wherein the diepoxide is selected from the group diepoxide based on diglycidyl ether of bisphenol A, bisphenol F or a mixture of both.

A polymer according to any one of the preceding claims, wherein the diepoxide used is a mixture of diglycidyl ether of bisphenol A or bisphenol F, or a mixture of both, in combination with a diglycidyl ether based on cardanol. 10. A polymer according to any one of the preceding claims, wherein the diisocyanate is an aromatic diisocyanate,

1 1. Polymer according to one of the preceding claims, wherein the diisocyanate is tolylene diisocyanate (TDI), 1, 5-naphthylene diisocyanate (NDI), or diphenylmethane diisocyanate (MDI) or a mixture of at least two of these isocyanates.

12. A process for the preparation of a polymer according to any one of the preceding claims wherein

the epoxide and the catalyst are heated to the reaction temperature and then the diisocyanate is added.

13. A process for producing a polymer according to any one of claims 1 to 1 1, wherein the catalyst is dissolved in a solvent, is heated with the solvent to the reaction temperature, and

- A mixture of the diisocyanate is added with the epoxide.

14. The method of claim 12 or 13, wherein the reaction is carried out in the absence of oxygen. 15. The method according to any one of the preceding claims, wherein the reaction temperature in a range of 140 ° C to 220 ° C, more preferably 150 ° C to 200 ° C and particularly preferably 160 ° C to 180 ° C.

16. The method according to any one of the preceding claims, wherein the molar ratio of the diepoxide to the diisocyanate in a range between 1, 0: 0.5 to 0.5: 1, 0, preferably between 1, 0: 0.9 to 0.9 : 1, 0 and more preferably at 1, 0: 1, 0.

17. The method according to any one of the preceding claims, wherein the catalyst concentration is 0.05 mol% to 5.0 mol% based on epoxide groups of the diepoxide, preferably 0.05 mol% to 1 mol%, and particularly preferably 0 , 05 mol% to 0.5 mol%.

18. The method according to any one of the preceding claims, wherein the concentration of the co-catalyst is 0.01 mol% to 1000 mol% based on epoxide groups of the diepoxide, preferably 0.05 mol% to 100 mol% and particularly preferably 0 , 05 mol% to 1 mol%.

19. Use of a polymer according to any one of claims 1 to 1 1 for the production of a shaped article by injection molding, calendering, powder sintering, laser sintering, melt pressing or extrusion; or as a modifier for thermoplastic material.